US4351777A - Preparation of fluorobenzonitriles - Google Patents
Preparation of fluorobenzonitriles Download PDFInfo
- Publication number
- US4351777A US4351777A US06/304,627 US30462781A US4351777A US 4351777 A US4351777 A US 4351777A US 30462781 A US30462781 A US 30462781A US 4351777 A US4351777 A US 4351777A
- Authority
- US
- United States
- Prior art keywords
- sub
- amine
- tris
- formula
- equal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title claims description 12
- 239000003352 sequestering agent Substances 0.000 claims abstract description 13
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims abstract description 12
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 7
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 5
- 239000012429 reaction media Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 20
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical group [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 12
- HPRCCXIECBBMPJ-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxy]-n,n-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]ethanamine Chemical compound COCCOCCOCCN(CCOCCOCCOC)CCOCCOCCOC HPRCCXIECBBMPJ-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000011698 potassium fluoride Substances 0.000 claims description 7
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 6
- 235000003270 potassium fluoride Nutrition 0.000 claims description 6
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- NHWQMJMIYICNBP-UHFFFAOYSA-N 2-chlorobenzonitrile Chemical compound ClC1=CC=CC=C1C#N NHWQMJMIYICNBP-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 claims description 4
- CAYDJHOYFLLLLM-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]-n,n-bis[2-[2-(2-ethoxyethoxy)ethoxy]ethyl]ethanamine Chemical compound CCOCCOCCOCCN(CCOCCOCCOCC)CCOCCOCCOCC CAYDJHOYFLLLLM-UHFFFAOYSA-N 0.000 claims description 3
- GDHXJNRAJRCGMX-UHFFFAOYSA-N 2-fluorobenzonitrile Chemical compound FC1=CC=CC=C1C#N GDHXJNRAJRCGMX-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- UTHAOIUUIWZHTP-UHFFFAOYSA-N 2-(1-methoxypropan-2-yloxy)-n,n-bis[2-(1-methoxypropan-2-yloxy)ethyl]ethanamine Chemical compound COCC(C)OCCN(CCOC(C)COC)CCOC(C)COC UTHAOIUUIWZHTP-UHFFFAOYSA-N 0.000 claims description 2
- RULYNRDLKTTWGC-UHFFFAOYSA-N 2-(2-butoxyethoxy)-n,n-bis[2-(2-butoxyethoxy)ethyl]ethanamine Chemical compound CCCCOCCOCCN(CCOCCOCCCC)CCOCCOCCCC RULYNRDLKTTWGC-UHFFFAOYSA-N 0.000 claims description 2
- XZGIHWAIIZHXKX-UHFFFAOYSA-N 2-(2-ethoxyethoxy)-n,n-bis[2-(2-ethoxyethoxy)ethyl]ethanamine Chemical compound CCOCCOCCN(CCOCCOCC)CCOCCOCC XZGIHWAIIZHXKX-UHFFFAOYSA-N 0.000 claims description 2
- XGLVDUUYFKXKPL-UHFFFAOYSA-N 2-(2-methoxyethoxy)-n,n-bis[2-(2-methoxyethoxy)ethyl]ethanamine Chemical compound COCCOCCN(CCOCCOC)CCOCCOC XGLVDUUYFKXKPL-UHFFFAOYSA-N 0.000 claims description 2
- YLZHYYKWIIHFLZ-UHFFFAOYSA-N 2-(2-propoxyethoxy)-n,n-bis[2-(2-propoxyethoxy)ethyl]ethanamine Chemical compound CCCOCCOCCN(CCOCCOCCC)CCOCCOCCC YLZHYYKWIIHFLZ-UHFFFAOYSA-N 0.000 claims description 2
- GAOZDOLDFJFIBO-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]-n,n-bis[2-[2-(2-butoxyethoxy)ethoxy]ethyl]ethanamine Chemical compound CCCCOCCOCCOCCN(CCOCCOCCOCCCC)CCOCCOCCOCCCC GAOZDOLDFJFIBO-UHFFFAOYSA-N 0.000 claims description 2
- CMGGYFAMOBSZDP-UHFFFAOYSA-N 2-[2-(2-propoxyethoxy)ethoxy]-n,n-bis[2-[2-(2-propoxyethoxy)ethoxy]ethyl]ethanamine Chemical compound CCCOCCOCCOCCN(CCOCCOCCOCCC)CCOCCOCCOCCC CMGGYFAMOBSZDP-UHFFFAOYSA-N 0.000 claims description 2
- AZBZSIZLBRMZFW-UHFFFAOYSA-N 2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]-n,n-bis[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethyl]ethanamine Chemical compound COCCOCCOCCOCCN(CCOCCOCCOCCOC)CCOCCOCCOCCOC AZBZSIZLBRMZFW-UHFFFAOYSA-N 0.000 claims description 2
- QYOCMIVPWWBWGX-UHFFFAOYSA-N 2-methoxy-n,n-bis(2-methoxyethyl)ethanamine Chemical compound COCCN(CCOC)CCOC QYOCMIVPWWBWGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910020543 Cm H2m+1 Inorganic materials 0.000 claims description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 13
- BNBRIFIJRKJGEI-UHFFFAOYSA-N 2,6-difluorobenzonitrile Chemical compound FC1=CC=CC(F)=C1C#N BNBRIFIJRKJGEI-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- XPTAYRHLHAFUOS-UHFFFAOYSA-N 2-chloro-6-fluorobenzonitrile Chemical compound FC1=CC=CC(Cl)=C1C#N XPTAYRHLHAFUOS-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- -1 for example Substances 0.000 description 6
- AEKVBBNGWBBYLL-UHFFFAOYSA-N 4-fluorobenzonitrile Chemical compound FC1=CC=C(C#N)C=C1 AEKVBBNGWBBYLL-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- OHDYZVVLNPXKDX-UHFFFAOYSA-N 2,3-dichlorobenzonitrile Chemical compound ClC1=CC=CC(C#N)=C1Cl OHDYZVVLNPXKDX-UHFFFAOYSA-N 0.000 description 1
- LJFDXXUKKMEQKE-UHFFFAOYSA-N 2,4-difluorobenzonitrile Chemical compound FC1=CC=C(C#N)C(F)=C1 LJFDXXUKKMEQKE-UHFFFAOYSA-N 0.000 description 1
- KUWBYWUSERRVQP-UHFFFAOYSA-N 3,4-dichlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1Cl KUWBYWUSERRVQP-UHFFFAOYSA-N 0.000 description 1
- CHKLNKWJIDQKFV-UHFFFAOYSA-N 3-chloro-2-fluorobenzonitrile Chemical compound FC1=C(Cl)C=CC=C1C#N CHKLNKWJIDQKFV-UHFFFAOYSA-N 0.000 description 1
- VAHXXQJJZKBZDX-UHFFFAOYSA-N 3-chloro-4-fluorobenzonitrile Chemical compound FC1=CC=C(C#N)C=C1Cl VAHXXQJJZKBZDX-UHFFFAOYSA-N 0.000 description 1
- GJNGXPDXRVXSEH-UHFFFAOYSA-N 4-chlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1 GJNGXPDXRVXSEH-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
Definitions
- the present invention relates to the preparation of fluorobenzonitriles, and, more espcially, to the preparation of fluorobenzonitriles from their corresponding chlorobenzonitriles by reaction of the latter with an alkali metal fluoride.
- a major object of the present invention is the provision of an improved process for the preparation of fluorobenzonitriles, which process can be conducted much more rapidly vis-a-vis those known to the art, is more valuable on an industrial scale, and is far more productive in the preparation of those fluorobenzonitriles useful as intermediates in the preparation of various phytosanitary compounds and pharmaceuticals.
- the present invention features a process for the preparation of fluorobenzonitriles by reacting their corresponding chlorobenzonitriles with at least one alkali metal fluoride, in an aprotic solvent reaction medium, in the presence of at least one tertiary amine sequestering agent having the structural formula:
- R 1 , R 2 , R 3 , R 4 which may be identical or different, each represents a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms and R 5 represents an alkyl or cycloalkyl radical having from 1 to 12 carbon atoms, a phenyl radical or a radical of the formula --C m H 2m --, or C m H 2m+1 -- ⁇ --, with m ranging from 1 to about 12 and ⁇ being phenyl.
- a sequestering agent of the formula (I) is used in which R 1 , R 2 , R 3 and R 4 represent a hydrogen atom or a methyl radical, R 5 and n being as above-defined.
- n is greater than or equal to 0 and less than or equal to 6 and in which R 5 represents an alkyl radical having from 1 to 4 carbon atoms.
- French Pat. No. 1,302,365 describes the preparation of the tertiary amines N--(CH 2 --CH 2 --O--CH 3 ) 3 and N--(CH 2 --CH 2 --O--CH 2 --CH 2 --O--CH 3 ) 3 as by-products from the synthesis of the corresponding primary and secondary amines, such primary and secondary amines being valuable as intermediates in the synthesis of various pharmaceuticals, as corrosion inhibitors, as intermediates in the synthesis of agricultural chemicals, and as emulsifiers.
- the prior art including the aforenoted French Pat. No. 1,302,365, is conspicuously devoid of any suggestion that the topic amines could be utilized in any reaction within the ambit of this invention.
- the fluorobenzonitriles advantageously prepared according to this invention have the structural formula: ##STR3## wherein n and m are integers greater than or equal to 1 and less than or equal to 5.
- the subject fluorobenzonitriles are prepared from chlorobenzonitriles having the structural formula: ##STR4## wherein n is as above defined.
- the more preferred fluorobenzonitriles according to the present invention are those in which n and m are greater than or equal to 1 and less than or equal to 3, and wherein the fluorine atoms are in the ortho- and/or para-position.
- chlorobenzonitriles employed in the process of the invention may comprise, in addition, substituents that are inert under the conditions of the reaction, such as the CF 3 and alkyl radicals, for example.
- the alkali metal fluorides that may be employed within the scope of the present invention principally, are potassium fluoride and/or cesium fluoride and/or rubidium fluoride.
- the alkali metal fluorides must be used in their anhydrous form.
- the solvent is preferably selected from among N-methylpyrrolidone, dimethylsulfoxide, dimethylformamide and sulfolane.
- Sulfolane is particularly preferred.
- the selection of the sequestering agent most suitable for any particular embodiment of the invention is made by taking into consideration the size of the alkali metal cation of the alkali metal fluoride used. The greater the size of the cation, the larger the number of oxygen atoms contained in the molecule of the sequestering agent must be.
- potassium fluoride when potassium fluoride is used, for example, it is preferred to employ as the sequestering agent, tris-(3,6,9-trioxadecyl)-amine, and/or tris-(3,6,9-trioxaundecyl)-amine.
- the process according to the invention is preferably carried out at a temperature between 180° C. and approximately 250° C., the temperature decreasing with increasing numbers of chlorine atoms in the starting material chlorobenzonitrile.
- the amount of the alkali metal fluoride to be used obviously depends upon the number of chlorine atoms to be replaced by fluorine.
- the reaction is carried out with a 10 to 50 molar % excess, with respect to stoichiometry.
- an amount of solvent is used such that the molar ratio of the solvent to the starting material chlorobenzonitrile ranges from approximately 1 to approximately 50, and preferably ranges from approximately 2 to approximately 20.
- reaction mixture was heated to 220° C. under agitation for 24 hours, then was cooled and filtered.
- reaction mixture was heated under agitation to 210° C. After 3 hours, 20 min. of reaction at 210° C., the chromatographic analysis of the reaction mixture yielded the following composition:
- the reaction mixture was heated under agitation to 210° C.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8020573 | 1980-09-25 | ||
| FR8020573A FR2490634A1 (fr) | 1980-09-25 | 1980-09-25 | Procede de preparation de fluorobenzonitriles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4351777A true US4351777A (en) | 1982-09-28 |
Family
ID=9246275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/304,627 Expired - Fee Related US4351777A (en) | 1980-09-25 | 1981-09-22 | Preparation of fluorobenzonitriles |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4351777A (enrdf_load_stackoverflow) |
| EP (1) | EP0049186B1 (enrdf_load_stackoverflow) |
| JP (1) | JPS5824430B2 (enrdf_load_stackoverflow) |
| DE (1) | DE3160603D1 (enrdf_load_stackoverflow) |
| FR (1) | FR2490634A1 (enrdf_load_stackoverflow) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4952719A (en) * | 1984-10-15 | 1990-08-28 | Occidental Chemical Corporation | Process for the preparation of halo aromatic compounds |
| US5466859A (en) * | 1993-07-21 | 1995-11-14 | Hoechst Aktiengesellschaft | Process for preparing fluorobenzonitriles |
| US5502235A (en) * | 1994-12-28 | 1996-03-26 | Dowelanco | Solventless process for making 2,6 difluorobenzonitrile |
| US20030110320A1 (en) * | 2001-12-12 | 2003-06-12 | Takatsugu Ono | Information processing apparatus |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59190087A (ja) * | 1983-04-12 | 1984-10-27 | Sanshin Ind Co Ltd | スロツトル開度検出器の船外機用エンジンへの取付構造 |
| JPS6290951U (enrdf_load_stackoverflow) * | 1985-11-28 | 1987-06-10 | ||
| DE59407426D1 (de) * | 1993-07-21 | 1999-01-21 | Clariant Gmbh | Verfahren zur Herstellung von Fluorbenzonitrilen |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3290353A (en) * | 1963-04-01 | 1966-12-06 | Diamond Alkali Co | Halogenated aromatic nitriles |
| US4229365A (en) * | 1977-05-28 | 1980-10-21 | Basf Aktiengesellschaft | Manufacture of substituted fluorobenzenes |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IE47471B1 (en) * | 1977-10-31 | 1984-03-21 | Merck & Co Inc | Method of preparing 2,4-difluoroaniline |
| FR2423478A1 (fr) * | 1978-04-21 | 1979-11-16 | Rhone Poulenc Ind | Nouveau procede de preparation de tris(polyoxaalkyl)amines |
| FR2423477A1 (fr) * | 1978-04-21 | 1979-11-16 | Rhone Poulenc Ind | Nouveau procede de preparation de la tris(hydroxy-8 dioxa-3,6 octyl)amine |
-
1980
- 1980-09-25 FR FR8020573A patent/FR2490634A1/fr active Granted
-
1981
- 1981-09-16 DE DE8181401437T patent/DE3160603D1/de not_active Expired
- 1981-09-16 EP EP81401437A patent/EP0049186B1/fr not_active Expired
- 1981-09-22 JP JP56148904A patent/JPS5824430B2/ja not_active Expired
- 1981-09-22 US US06/304,627 patent/US4351777A/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3290353A (en) * | 1963-04-01 | 1966-12-06 | Diamond Alkali Co | Halogenated aromatic nitriles |
| US4229365A (en) * | 1977-05-28 | 1980-10-21 | Basf Aktiengesellschaft | Manufacture of substituted fluorobenzenes |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4952719A (en) * | 1984-10-15 | 1990-08-28 | Occidental Chemical Corporation | Process for the preparation of halo aromatic compounds |
| US5466859A (en) * | 1993-07-21 | 1995-11-14 | Hoechst Aktiengesellschaft | Process for preparing fluorobenzonitriles |
| US5502235A (en) * | 1994-12-28 | 1996-03-26 | Dowelanco | Solventless process for making 2,6 difluorobenzonitrile |
| US20030110320A1 (en) * | 2001-12-12 | 2003-06-12 | Takatsugu Ono | Information processing apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3160603D1 (en) | 1983-08-18 |
| JPS5824430B2 (ja) | 1983-05-20 |
| FR2490634A1 (fr) | 1982-03-26 |
| FR2490634B1 (enrdf_load_stackoverflow) | 1983-10-21 |
| EP0049186A1 (fr) | 1982-04-07 |
| JPS5782359A (en) | 1982-05-22 |
| EP0049186B1 (fr) | 1983-07-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: RHONE-POULENC INDUSTRIES, 22, AVENUE MONTAIGNE, 75 Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:RAMANADIN, R.;ROUSTAN, ALAIN;SOULA, GERARD;REEL/FRAME:003925/0307 Effective date: 19810907 |
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| MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, PL 96-517 (ORIGINAL EVENT CODE: M170); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 4 |
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| FEPP | Fee payment procedure |
Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
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| LAPS | Lapse for failure to pay maintenance fees | ||
| STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
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| FP | Lapsed due to failure to pay maintenance fee |
Effective date: 19900930 |